EP2999754A1 - Composition de revêtement pour surfaces métalliques ayant des propriétés améliorées de résistance à la corrosion - Google Patents

Composition de revêtement pour surfaces métalliques ayant des propriétés améliorées de résistance à la corrosion

Info

Publication number
EP2999754A1
EP2999754A1 EP14733345.4A EP14733345A EP2999754A1 EP 2999754 A1 EP2999754 A1 EP 2999754A1 EP 14733345 A EP14733345 A EP 14733345A EP 2999754 A1 EP2999754 A1 EP 2999754A1
Authority
EP
European Patent Office
Prior art keywords
active substance
containers
nano
functionalized nano
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP14733345.4A
Other languages
German (de)
English (en)
Other versions
EP2999754B1 (fr
Inventor
Brunetto Martorana
Davide RONCATO
Daniele Bassan
Elisa MICUCCI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centro Ricerche Fiat SCpA
Original Assignee
Centro Ricerche Fiat SCpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centro Ricerche Fiat SCpA filed Critical Centro Ricerche Fiat SCpA
Publication of EP2999754A1 publication Critical patent/EP2999754A1/fr
Application granted granted Critical
Publication of EP2999754B1 publication Critical patent/EP2999754B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4476—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications comprising polymerisation in situ
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm

Definitions

  • the present invention relates to a coating composition for metal surfaces, in particular, for protecting metal surfaces from corrosion. More specifically, the present invention relates to a composition for at least partially coating the bodywork and/or chassis of motor vehicles.
  • Corrosion is one of the main phenomena responsible for the progressive deterioration of metal structures and even their destruction.
  • the corrosive effects of certain atmospheric agents can have a very significant influence on useful life of a motor vehicle or, at the least, on some of its components .
  • the compositions illustrated therein comprise particles of antioxidant materials dispersed in a polymer matrix.
  • steel sheet metal panels are subjected to a galvanization process , via which a thin layer of zinc is formed on the surface that provides protection against cathodic corrosion of the panel.
  • a polymer layer approximately 5 ⁇ thick is deposited on this base, which provides the galvanized steel with temporary corrosion protection.
  • electrically conductive pigments for example based on zinc or iron phosphide, are introduced into the polymer matrix to facilitate spot welding in the phase of forming and assembling the bodywork or the chassis of the motor vehicle.
  • Corrosion resistance is further improved by means of a phosphate coating process and the surface is prepared for the next treatment of electrophoretic deposition (cataphoresis) .
  • the latter consists in the application of a further protective layer by means of immersion in a bath comprising, in general terms, a polymer resin and a plurality of agents (e.g. pigments, extenders and solvents).
  • a further protective layer by means of immersion in a bath comprising, in general terms, a polymer resin and a plurality of agents (e.g. pigments, extenders and solvents).
  • the resin is selected to be water soluble in weakly acidic environments, so as to form a fairly stable suspension of micelles.
  • the solvents are generally of two types: polar solvents soluble in water and water- insoluble solvents, which interact with the resin micelles, affecting the thickness of the applied film.
  • Pigments and extenders generally inorganic, determine the colour, appearance and corrosion resistance of the product. They are absorbed into the resin micelles during the preparation of the paint.
  • the actual deposition is obtained by applying an electrical potential (to the chassis) , which causes the migration of the micelles towards the metal surface and the subsequent solidification of the coating, which is then usually polymerized in an oven.
  • the coating obtained with this procedure performs a function of primary protection against corrosion.
  • primer which performs two functions: on one hand it protects the layer deposited by cataphoresis from potential damage caused by exposure to UV radiation (as a rule, an opaque primer is therefore normally used) , while on the other, it constitutes the base for the subsequent application of a layer (possibly applied in several coats) containing coloured pigments, possibly with added agents to provide effects such as metalized, pearlescent, etc.
  • the main manufacturers in the automotive sector feel the need to improve the performance of the coatings even further in terms of corrosion resistance , in particular with reference to the sharp edges and cavities commonly present in the bodywork and chassis of a motor vehicle .
  • the need is felt within the sector to provide new technologies that enable reducing the number and complexity of steps of the coating process , the thicknesses and other operating parameters , while maintaining or even improving the quality of corrosion protection, especially in certain critical areas .
  • the need is particularly felt for providing new coating compositions that possess self-healing abilities, so as to increase the durability of the corrosion protection and that of the coating in general .
  • An obj ect of the present invention is therefore that of providing a coating composition for metal surfaces , in particular for at least partially coating a motor vehicle' s bodywork and/or chassis, capable of satisfying at least one of the above-stated needs .
  • a coating composition for metal surfaces according to claim 1.
  • a coating composition is provided for metal surfaces .
  • the coating c is provided for metal surfaces .
  • composition for metal surfaces comprises a matrix (for example, a polymer resin) and at least first and second functionalized nano-containers dispersed within the matrix.
  • a matrix for example, a polymer resin
  • first and second functionalized nano-containers dispersed within the matrix.
  • the term "functionalized nano- container” means a volume of nanometric size containing an active substance confined within a porous core and/or a porous shell that, in normal conditions, prevent direct contact of the active substance with the external environment, but that, in the presence of an opportune trigger (defined by predetermined environmental conditions, such as a change in H, ionic strength, humidity, brightness, temperature, mechanical stress or even activation of a magnetic or electromagnetic field) , enable the release of the active substance into the external environment.
  • an opportune trigger defined by predetermined environmental conditions, such as a change in H, ionic strength, humidity, brightness, temperature, mechanical stress or even activation of a magnetic or electromagnetic field
  • the first and the second functionalized nano-containers advantageously contain respective active substances different from each other.
  • the first functionalized nano-containers contain a corrosion inhibitor agent as the active substance, which is able to suppress corrosion and delamination processes that typically occur around defects or sharp edges.
  • the second functionalized nano-containers contain one of the following as the active substance:
  • a precursor of a polymerizable species able to form a thin polymeric layer such as to cover a damaged area and/or repair a damaged layer and/or to prevent the propagation of a crack or other defect .
  • the second functionalized nano-containers can comprise a core immiscible or poorly miscible in water and dispersible in an aqueous medium, or a core miscible in water and dispersible in a non-aqueous medium, and an active substance soluble in the core selected from sealants, lubricants, anti- fouling agents, hydrophobic materials (water displacement function), or even monomers and adhesives .
  • the first and second nano-containers have sizes between 1 and 1000 nm and comprise a polymer or polyelectrolyte shell (for example, composed of multilayer electrolytic structure obtained via a layer-by- layer, or LbL, deposition technique) such as to have permeability that is variable in response to an environmental factor such as a change in H, ionic strength, humidity, brightness, temperature, or even activation of a magnetic or electromagnetic field.
  • a polymer or polyelectrolyte shell for example, composed of multilayer electrolytic structure obtained via a layer-by- layer, or LbL, deposition technique
  • an environmental factor such as a change in H, ionic strength, humidity, brightness, temperature, or even activation of a magnetic or electromagnetic field.
  • the shell of the first nano-containers is sensitive to change in pH, given that, as is known, corrosion phenomena are typically associated with localized changes in pH in the anode and cathode areas .
  • the polymer shell for example, gelatinous or polyelectrolyte shell (for example, based on poly (allylamine) and/or polystyrene sulfonate) can form a nano-capsule inside which a corrosion inhibitor can be contained (for example, quinaldic acid, mercaptobenzothiazole or derivatives) .
  • this shell could form the coating of a nanometric-scale sublayer, such as, for example , nanometric particles of metals or metal oxides , synthetic or natural nanotubes (for example, aluminosilicates) .
  • a nanometric-scale sublayer such as, for example , nanometric particles of metals or metal oxides , synthetic or natural nanotubes (for example, aluminosilicates) .
  • natural nanotubes based on halloysite or even nano-composites of the layered double hydroxide (LDH) type for example LDH Al-Zn, can be advantageously used.
  • LDH layered double hydrox
  • the substrate can be porous or hollow and the inhibitor can be incorporated in the cavity or the pores of the substrate or in the shell, in which case the substrate only acts as a support for the polymer or electrolyte shell.
  • support substrates can be materials commonly used in coating compositions, such as, for example, nano-particles of silica, zirconium, etc.
  • the polymer or polyelectrolyte shell of the first nano- containers can comprise one or more layers of a suitable polymer or polyelectrolyte that is sensitive to a trigger factor and able to release the corrosion inhibitor in response to a given variation in this trigger factor.
  • the polymer or polyelectrolyte can, for example, be selected from the group composed of polyalkylene imines, polystyrene sulfonate, poly (allylamine) , polyvinyl alcohol, polystyrene, polyalkylene glycol, biopolymers and poly-amino acids, such as gelatine, agarose, cellulose, alginic acid, casein, polyarginine , polyglycine and polyaspartic acid, or derivatives obtained by modifying these compounds or introducing specific functional groups according to known methods.
  • These groups for example, can give the polymer or polyelectrolyte shell desirable properties such as hydrophily, hydrophobia, electrical charge, sensitivity to a given trigger factor, etc.
  • the polymer or polyelectrolyte shell could also comprise copolymers or mixtures of polymers or polyelectrolytes .
  • the composition enables freeing the active substances, and the corrosion inhibitor agent in particular, only after a specific trigger condition, caused for example by the formation of scratches that allow the penetration of corrosive agents .
  • This composition therefore constitutes a protective layer that can be activated following trigger events, thereby creating a further corrosion barrier.
  • the composition preferably comprises third functionalized nano- containers containing, as the active substance, one of the following that is not contained as the active substance in the second functionalized nano- containers :
  • a precursor of a polymerizable species able to form a thin polymeric layer such as to cover a damaged area and/or repair a damaged layer and/or prevent the propagation of a crack or other defect ;
  • the composition also comprises nano- traps able to incorporate certain potentially harmful , aggressive or corrosive molecules (for example , molecules of water, corrosive anions , etc . ) .
  • nano- trap means a volume of nanometric size defined in a porous core and/or shell that , when the concentration of certain chemical species exceeds a given threshold value , is able to selectively absorb these species , preventing them from returning to the external environment .
  • the nano- traps can be substantially formed by a shell of an empty nano- container .
  • they can be formed by particles of swelling clays .
  • structured and LDH cationic clays can be used for the nano- traps .
  • the advantages that can be achieved therewith are evident.
  • the coating composition according to the present invention enables increasing the useful life of a metal structure (in particular the bodywork and/or chassis of a motor vehicle) , with a reduction in maintenance costs associated with reduced instances of corrosion, especially in the first period of the metal structure's life.
  • the coating composition according to the present invention is particularly effective in preventing corrosion around sharp edges and cavities.
  • the nano-containers were supplied in the form of an aqueous suspension. LDHs were used with nitrate groups obtained via calcination-rehydration of synthetic hydrotalcite. The dispersion properties were evaluated by introducing the nano-containers in demineralised water and in the pigment paste normally used for cataphoresis painting . GRAVIMETRIC TEST
  • a third treatment was then performed after having added a further 20 ml of demineralised water, keeping the system agitated following a pulsed profile (agitation for 60 seconds alternated with 60 seconds without agitation) .
  • a two-phase system was still obtained, but the dispersion of the nano- containers in the pigment paste can be considered satisfactory.
  • the nano-containers supplied in solid form (powder) , are formed by nano-capsules containing methylbenzotriazole as a corrosion inhibitor .
  • the nano-containers were supplied in the form of an aqueous suspension (solid content equal to 18.3% by weight) and formed by LDH containing methylbenzotriazole, a corrosion inhibitor, as the active substance. 5.55 g of nano -containers were introduced into 6 g of pigment paste. Due to the viscosity being too high, agitation of the system was not possible, and so 10 ml of demineralised water was added. The thus obtained suspension was agitated and sonified with the 6 -mm-diameter probe for 10 minutes at 20% power.
  • the nano-containers were supplied in the form of an aqueous suspension (solid content equal to 27% by weight) and formed by LDH containing methylbenzotriazole, a corrosion inhibitor, as the active substance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Nanotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Molecular Biology (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition de revêtement pour des surfaces métalliques comprenant une matrice polymère et au moins des premiers et seconds nano-conteneurs fonctionnalisés dispersés dans la matrice et contenant respectivement des substances actives différentes l'une de l'autre. Chacun desdits premiers et seconds nano-conteneurs fonctionnalisés définit un volume de taille nanométrique contenant ladite substance active confinée au sein d'un noyau poreux et/ou d'une coque poreuse qui, dans des conditions normales, empêchent le contact direct de la substance active avec l'environnement externe, tout en, dans des conditions de déclenchement prédéterminées, permettant la libération de la substance active dans l'environnement externe. Les premiers nano-conteneurs fonctionnalisés contiennent un agent inhibiteur de corrosion comme substance active, tandis que les seconds nano-conteneurs fonctionnalisés contiennent soit un agent capable de déplacer l'eau soit un précurseur d'une espèce polymérisable, capable de former une couche polymère afin de recouvrir une zone endommagée et/ou d'empêcher la propagation d'une fissure ou d'un autre défaut, comme substance active.
EP14733345.4A 2013-05-23 2014-05-23 Composition de revêtement pour surfaces métalliques ayant des propriétés améliorées de résistance à la corrosion Active EP2999754B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000416A ITTO20130416A1 (it) 2013-05-23 2013-05-23 Composizione di rivestimento per superfici metalliche con migliorate proprieta' anticorrosione
PCT/IB2014/061667 WO2014188390A1 (fr) 2013-05-23 2014-05-23 Composition de revêtement pour surfaces métalliques ayant des propriétés améliorées de résistance à la corrosion

Publications (2)

Publication Number Publication Date
EP2999754A1 true EP2999754A1 (fr) 2016-03-30
EP2999754B1 EP2999754B1 (fr) 2017-07-19

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP14733345.4A Active EP2999754B1 (fr) 2013-05-23 2014-05-23 Composition de revêtement pour surfaces métalliques ayant des propriétés améliorées de résistance à la corrosion

Country Status (5)

Country Link
US (1) US20160090487A1 (fr)
EP (1) EP2999754B1 (fr)
CN (1) CN105408431B (fr)
IT (1) ITTO20130416A1 (fr)
WO (1) WO2014188390A1 (fr)

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US10619056B2 (en) 2015-09-03 2020-04-14 Ppg Industries Ohio, Inc. Corrosion inhibitors and coating compositions containing the same
US10246594B2 (en) 2016-07-20 2019-04-02 The Boeing Company Corrosion inhibitor-incorporated layered double hydroxide and sol-gel coating compositions and related processes
US10428226B2 (en) 2016-07-20 2019-10-01 The Boeing Company Sol-gel coating compositions and related processes
US10246593B2 (en) 2016-07-20 2019-04-02 The Boeing Company Sol-gel coating compositions including corrosion inhibitor-encapsulated layered double hydroxide and related processes
US10421869B2 (en) 2017-01-09 2019-09-24 The Boeing Company Sol-gel coating compositions including corrosion inhibitor-encapsulated layered metal phosphates and related processes
WO2018160203A1 (fr) * 2017-03-01 2018-09-07 Ppg Industries Ohio, Inc. Inhibiteurs de corrosion et compositions de revêtement les contenant
WO2018183060A1 (fr) 2017-03-28 2018-10-04 The Texas A&M University System Revêtements pour matériaux
WO2019034915A1 (fr) * 2017-08-17 2019-02-21 Khalifa University of Science and Technology Revêtements de nanocontenants à base de carbone mésoporeux pour la protection contre la corrosion de structures métalliques
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WO2022146168A1 (fr) * 2020-12-30 2022-07-07 Общество С Ограниченной Ответственностью "Научно-Производственное Объединение "Минералика" Revêtement nanocomposite comprenant des nano-conteneurs minéraux

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Also Published As

Publication number Publication date
ITTO20130416A1 (it) 2014-11-24
CN105408431A (zh) 2016-03-16
WO2014188390A1 (fr) 2014-11-27
EP2999754B1 (fr) 2017-07-19
CN105408431B (zh) 2017-12-12
US20160090487A1 (en) 2016-03-31

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